Copolymer for cosmetic preparation

ABSTRACT

The polymer for cosmetics produced by polymerizing (A) a fluorine-containing (meth)acrylate, and (B) at least one silicon-containing polymerizable compound selected from the group consisting of a mercapto-modified silicone, an azo group-containing silicone and a polymerizable silane can be blended easily in cosmetic preparations and can form a film excellent in a water proofing property, a water- and oil-repellency, feelings in use and safety. This copolymer for cosmetics can improve the drawbacks of fluorine compound-treated powders.

FIELD OF THE INVENTION

The present invention relates to a copolymer for cosmetics which can beblended easily in a cosmetics preparation and is excellent in awaterproofing property, a water- and oil-repellency, feelings in use andsafety, and to cosmetics characterized by containing the copolymer. Thecopolymer functions as a film-forming agent for cosmetics, acompatibilizer and emulsifier for a fluorine-containing raw material anda fluorine-free raw material, and a surface-treatment agent for fluorinecompound-treated powders and silicone-treated powders.

RELATED ART

Heretofore, hydrocarbon-based emulsion resins have been used asfilm-forming agents for cosmetics. These are blended for the purpose ofholding pigments or effective components in preparations on the skin fora long period of time by forming films after their application. However,because of their insufficient waterproofing properties and water- andoil-repellency, they are disadvantageous in that the films are broken bythe contact with water or by sweat or sebum excreted from the skin. Inaddition, an acryl-silicone copolymer which has improved the drawbacksin the waterproofing property and the water-repellency of thehydrocarbon-based emulsion resins is in use recently (Japanese PatentKokai Publication No. 2-247110 (247110/1990)). This is a copolymer ofhydrocarbon-based acrylate and a silicone macromonomer, a film thereofbeing excellent in the waterproofing property and the water-repellency.

However, since the acryl-silicone copolymer also has low oil-repellency,it can not prevent the coming off of make-up caused by sebum. On theother hand, there is known a technique which contains a copolymer of analkyl (meth)acrylate having a long-chain alkyl group having 8 or morecarbon atoms and a polyfluoroalkyl (meth)acrylate having apolyfluoroalkyl group having 4 or more carbon atoms as a film-formingcomponent in order to imparting the oil-repellency (Japanese PatentKokoku Publication No. 3-46444 (46444/1991)). However, since thiscopolymer has a higher softening temperature than the skin temperature,it does not form any film in the form of emulsion dispersing in water. Acopolymer having such a reduced molecular weight that the copolymer candissolve in a solvent in order to form a film has no oil-repellency.

On the other hand, fluorine-containing raw materials such as a fluorinecompound-treated powder and perfluoropolyether have recently come to beblended in cosmetic preparations. Since these fluorine-containing rawmaterials have poor affinities with fluorine-free raw materials such asthose of hydrocarbon type and of silicone type which have been usedwidely, it is very difficult to blend them in preparations withstability. Therefore, the development of compatibilizers for theimprovement in affinities between fluorine-containing raw materials andfluorine-free raw materials has been demanded.

SUMMARY OF THE INVENTION

According to the present invention, an intensive study for solving theabove problems has made clear that when a fluorine-containing(meth)acrylate copolymer having a specific composition is dissolved ordispersed in water or solvents, the copolymer exhibits excellentproperties as a copolymer for cosmetics. The copolymer for cosmetics ofthe present invention can be blended easily in conventional cosmeticpreparations, and the cosmetics in which the copolymer is blended canform films excellent in waterproofing properties, water- andoil-repellency, feelings in use and safety after their application onthe skin.

Furthermore, this copolymer for cosmetics serves as a compatibilizerbetween fluorine-containing raw materials and fluorine-free rawmaterials, whereby having the effect of stabilizing cosmeticpreparations.

The present invention provides a copolymer for cosmetics comprising

(A) 5 to 99 parts by weight of repeating units derived from afluorine-containing (meth)acrylate, and

(B) 95 to 1 parts by weight of repeating units derived from at least onesilicon-containing polymerizable compound selected from the groupconsisting of a mercapto-modified silicone, an azo group-containingsilicone and a polymerizable silane.

DETAILED DESCRIPTION OF THE INVENTION

The copolymer of the present invention may comprise (C) 1 to 50 parts byweight of repeating units derived from at least one fluorine-freemonomer selected from the group consisting of a polylakyleneglycol(meth)acrylate, an alkyl (meth)acrylate macromonomer and an alkyl(meth)acrylate, in addition to the repeating units (A) and (B).

The copolymer may be:

(i) a copolymer comprising the fluorine-containing (meth)acrylate andthe mercapto-modified silicone;

(ii) a copolymer comprising the fluorine-containing (meth)acrylate andthe azo group-containing silicone;

(iii) a copolymer comprising the fluorine-containing (meth) acrylate andthe polymerizable silane;

(iv) a copolymer comprising the fluorine-containing (meth) acrylate, atleast one silicon-containing polymerizable compound selected from thegroup consisting of mercapto-modified silicone, azo group-containingsilicone and polymerizable silane, and the polyalkyleneglycol(meth)acrylate;

(v) a copolymer comprising the fluorine-containing (meth)acrylate, atleast one silicon-containing polymerizable compound selected from thegroup consisting of the mercapto-modified silicone, the azogroup-containing silicone and the polymerizable silane, and the alkyl(meth)acrylate macromonomer; or

(vi) a copolymer comprising the fluorine-containing (meth)acrylate, atleast one silicon-containing polymerizable compound selected from thegroup consisting of the mercapto-modified silicone, the azogroup-containing silicone and the polymerizable silane, and the alkyl(meth)acrylate.

The fluorine-containing (meth)acrylate used for the copolymer forcosmetics has, for example, the following structural formula (I-1):

wherein Rf is a polyfluoroalkyl or perfluoropolyether group having 6 to16 carbon atoms,

A is an alkylene group having 1 to 4 carbon atoms or

wherein R¹ is an alkyl group having 1 to 4 carbon atoms and R² is analkylene group having 1 to 4 carbon atoms, or

and X is a hydrogen atom or a methyl group.

The fluorine-containing (meth)acrylate may be, for example, afluorine-containing (meth)acrylate macromonomer having the followingstructural formula (I-2):

wherein Rf is a polyfluoroalkyl or perfluoropolyether group having 6 to16 carbon atoms, A¹ is an alkylene group having 1 to 4 carbon atoms or

wherein R¹ is an alkyl group having 1 to 4 carbon atoms and R² is analkylene group having 1 to 4 carbon atoms, or

and X¹¹ is a hydrogen atom or a methyl group, Y¹¹ is a hydrogen atom ora methyl group and m is from 5 to 100.

The polyfluoroalkyl group (Rf group) may be a perfluoroalkyl group.

The perfluoropolyether group is specifically as follows:

F(CF(CF₃)CF₂O)_(n)CF₂CF₂—

wherein n is an integer of from 3 to 30,

CF₃O(CF(CF₃)CF₂O)_(n)(CF₂O)_(m)CF₂—

wherein n is an integer of from 2 to 30 and m is an integer of from 3 to70,

CF₃O(CF₂CF₂O)_(n)(CF₂O)_(m)CF₂—

wherein n is an integer of from 2 to 40 and m is an integer of from 4 to70, and

F(CF₂CF₂CF₂O)_(n)CF₂CF₂—

wherein n is an integer of from 3 to 30.

The number average molecular weight (determined by ¹⁹F-NMR) of theperfluoropolyether group is preferably in the range of from 500 to5,000.

Examples of the fluorine-containing (meth)acrylate are as follows:

CF₃(CF₂)₇(CH₂)OCOCH═CH₂,

CF₃(CF₂)₆(CH₂)OCOC(CH₃)═CH₂,

(CF₃)₂CF(CF₂)₆(CH₂)₂OCOCH═CH₂,

CF₃(CF₂)₇(CH₂)₂OCOC(CH₃)═CH₂,

CF₃(CF₂)₇(CH₂)₂OCOCH═CH₂,

HCF₂(CF₂)₇(CH₂)₂OCOCH═CH₂,

CF₃(CF₂)₅(CH₂)₂OCOCH═CH₂,

CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOCH═CH₂,

CF₃(CF₂)₇SO₂N(C₂H₅)(CH₂)₂OCOC(CH₃)═CH₂,

(CF₃)₂CF(CF₂)₆CH₂CH(OCOCH₃)CH_(2OCOC(CH) ₃)═CH₂,

(CF₃)₂CF(CF₂)₆CH₂CH(OH)CH₂OCOCH═CH₂,

F(CF(CF₃)CF₂O)₁₀CF₂CF₂—COOCH₂CH₂CH═CH₂,

These fluorine-containing (meth)acrylates may be used in admixtures ofat least two of them.

In the present invention, the silicon-containing polymerizable compoundwhich undergoes radical polymerization with the fluorine-containing(meth)acrylate is the mercapto-modified silicone, the azogroup-containing silicone or the polymerizable silane.

The mercapto-modified silicone is a silicone having at least one SHgroup. The mercapto-modified silicone has, for example, the followinggeneral formula (II-1- 1) or (II-1-2).

General formulas (II-1-1) and (II-1-2):

In the formulas, R¹ is a divalent saturated hydrocarbon group having alinear or branched carbon chain which may be intervened by one or twoether linkages, 1 is from 10 to 20, m is from 10 to 200 and n is from 1to 10.

Specific examples of the mercapto-modified silicone are as follows:

The azo group-containing silicone may be a silicone having an azo groupand a urethane linkage. The azo group-containing silicone has, forexample, the following general formula (II-2).

General formula (II-2):

In the formula, x is from 10 to 200 and n is from 1 to 20.

Specific examples of the azo group-containing silicone are as follows:

The polymerizable silane is a compound having an ethylenicallyunsaturated double bond and a siloxane bond. The polymerizable silanehas, for example, the following general formula (II-3-1) or (II-3-2):

or

CH₂═CHSi(OR³)₃  (II-3-2)

wherein R¹ is a methyl group or a hydrogen atom, R² is a divalentsaturated hydrocarbon group having a linear or branched carbon chainwhich may be intervened by one or two ether linkages, and R³ is an alkylgroup having 1 to 4 carbon atoms.

Specific examples of the polymerizable silane are as follows.

CH₂═CHSi(OCH₃)₃

These silicon-containing polymerizable compounds may be used inadmixtures of at least two of them.

In the present invention, when the mercapto-modified silicone or the azogroup-containing silicone is used, the silicone component bonds to theend of the fluorine-containing (meth)acrylate copolymer to give a blockor graft copolymer. Known general methods for synthesizing block orgraft copolymers include (1) a chain transfer method, (2) a polymerinitiator method, (3) a mechanical chemical reaction method, (4) abonding (addition, condensation) reaction method, (5) an exchangereaction method, (6) a living polymer method, (7) a group transferpolymerization method, (8) a iodine transfer polymerization method andthe like. The mercapto-modified silicone of the present invention givesblock or graft copolymers by (1) the chain transfer method, and the azogroup-containing silicone of the present invention gives block or graftcopolymers by (2) the polymer initiator method.

Although the block or graft copolymers can be produced even if any ofthe methods (1) to (8) is used, the methods other than the methods (1)and (2) have problems of having complicated operations or achieving lowyields. In the present invention, (1) the chain transfer method and (2)the polymer initiator method are preferably used, because they havefeatures of being easy to produce the polymers industrially and ofachieving high yields.

The polymer of the present invention may have (C) repeating unitsderived from at least one fluorine-free monomer selected from the groupconsisting of a polyalkyleneglycol (meth)acrylate, an alkyl(meth)acrylate macromonomer and an alkyl (meth)acrylate.

The polyalkyleneglycol (meth)acrylate has, for example, the followingstructural formula (III-1):

CH₂═CR¹¹COO—(R¹²—O)_(n)—R¹³  (III-1)

wherein R¹¹ and R¹³ are a hydrogen atom or a methyl group, R¹² is analkylene group having 2 to 6 carbon atoms and n is an integer of from 1to 50.

Specific examples thereof include 2-hydroxyethyl (meth)acrylate and

CH₂═C(CH₃)COO(CH₂CH₂O)_(n)H

wherein n is 2, 5 or 8.

The alkyl (meth)acrylate macromonomer has, for example, the followingstructural formula (III-2):

wherein X²¹ and y²¹ are a hydrogen atom or a methyl group, n is from 1to 22, and m is from 5 to 100.

Specific examples thereof include the followings:

The alkyl (meth)acrylate has, for example, the following structuralformula (III-3):

wherein X is a hydrogen atom or a methyl group and n is from 1 to 22(for example, from 1 to 10).

Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate,propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate,n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl(meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate and behenyl(meth)acrylate.

These fluorine-free monomers may be used in admixtures of at least twoof them.

In copolymers comprising a fluorine-containing monomer (namely,fluorine-containing (meth)acrylate) and a silicon-containingpolymerizable compound, the content of the fluorine-containing(meth)acrylate (A) preferably has a lower limit of 5% by weight, forexample, 10% by weight, particularly 20% by weight and an upper limit of99% by weight, for example, 95% by weight, particularly 80% by weight,based on the total amount of the fluorine-containing monomer and thesilicon-containing polymerizable compound. As the proportion of thesilicon-containing polymerizable compound in the copolymer becomeslarger, feelings in use of cosmetics in which the copolymer is blended,that is, a “sleek feeling” and a “dry feeling” become better andsolubility of the copolymer in fluorine-free solvents becomes higher.The amount of the silicon-containing polymerizable compounds (B)preferably has a lower limit of 1% by weight, for example, 5% by weight,particularly 20% by weight, and an upper limit of 95% by weight, forexample, 90% by weight, particularly 80% by weight, especially 50% byweight, based on the total amount of the fluorine-containing monomer andthe silicon-containing polymerizable compounds. The amount of thefluorine-free monomers (C) which are optionally used is from 0 to 50% byweight, for example, from 1 to 50% by weight, particularly from 2 to 30%by weight, based on the total amount of the fluorine-containing monomersand the silicon-containing polymerizable compounds,.

For improving the feeling in use and imparting functions other than thewaterproofing property and the water- and oil-repellency to films, othermonomer may be used together. Specific examples of the other monomerinclude glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, vinylchloride, vinylidene chloride and (meth)acrylic acid. The amount of theother monomer in a copolymer may be at most 20% by weight, for example,from 0.1 to 10% by weight relative to the copolymer.

When at least one of a hydrophilic group-containing monomer and/or anitrogen-containing monomer is used as the other monomer, the resultingcopolymer has good adsorbability to the hair and is suitable as acopolymer for hair cosmetics.

In the hair cosmetics, a copolymer having repeating units derived from(a) the fluorine-containing (meth)acrylate, (b) the silicon-containingpolymerizable compound and (c) the hydrophilic group-containing monomerand/or nitrogen-containing monomer is preferred. The weight ratio of(a):(b):(c) in the copolymer may be 10-90:10-90:0.1-20, preferably20-80:20-80:1-10.

The Rf group in the fluorine-containing (meth)acrylate particularlypreferred from the viewpoint of the feeling in use is aperfluoropolyether.

Examples of the hydrophilic group-containing monomer include(meth)acrylic acid and the aforementioned polyalkyleneglycol(meth)acrylate.

Examples of the nitrogen-containing monomer include (meth)acrylamide,N,N-dimethylacrylamide, (meth)acrylonitrile, N-vinylpyrrolidone,dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate,diacetone acrylamide, trimethylammonium chloride ethyl (meth)acrylate,methacryloyloxyethyttrimethylammonium chloride,2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, andmonomers having at least one urethane or urea linkage.

In particular, diacetone acrylamide and the monomers having at least oneurethane or urea linkage are preferred.

Examples of the monomers having at least one urethane or urea linkageinclude bis(acryloyloxyethyl)hydroxyethyl isocyanurate,tris(acryloyloxyethyl) isocyanurate,

wherein R is an alkyl group having 1 to 22 carbon atoms.

The fluorine-containing copolymer of the present invention can beproduced by bulk polymerization, solution polymerization and emulsionpolymerization. In the bulk polymerization, a method is adopted in whicha mixture of a fluorine-containing monomer and a silicon-containingpolymerizable compound is purged by nitrogen, a polymerization initiatoris then added, and the mixture is stirred in the range of from 40 to 80°C. for several hours to be polymerized. Alternatively, in the case ofthe solution polymerization, a mixture of the fluorine-containingmonomer and the silicon-containing polymerizable compound is dissolvedin a suitable organic solvent in which these monomers can dissolve andthen polymerized in the same manner as described earlier. The organicsolvent may be a hydrocarbon-based solvent, an ester-based solvent, aketone-based solvent, an alcohol-based solvent, a silicone-basedsolvent, a fluorine-containing solvent and the like.

In the case of the emulsion polymerization, the polymerization iscarried out in the same manner as described above after emulsifyingthese monomers in water using a proper emulsifier. In some combinationsof a fluorine-containing monomer and a silicon-containing polymerizablecompound, a poor compatibility of a fluorine-containing monomer and asilicon-containing polymerizable compound in water results in a poorcopolymerizability. In such a case, a method in which a proper auxiliarysolvent such as glycols and alcohols is added to improve thecompatibility of the monomers is adopted. A hydrophobic group in theemulsifier to be used in the emulsion polymerization may be any ofhydrocarbon type, silicon-containing type and fluorine-containing type.As for the ionicity of a hydrophilic group, any of nonionic one, anionicone, cationic one and amphoteric one may be used.

The polymerization initiator may be exemplified by various azo-type onesand peroxides. In the polymerization, a chain transfer agent or a pHmodifier may be added. The weight average molecular weight (measured byGPC) of the fluorine-containing copolymer obtained after thepolymerization is from 10,000 to 1,000,000, preferably from 20,000 to300,000.

A fluorine-containing copolymer prepared by solution polymerization oremulsion polymerization may be blended directly in the form of areaction liquid into cosmetic preparations. Alternatively, the polymermay be dissolved (or dispersed) in solvents (or water) after theisolation of only the polymers.

Although the fluorine-containing copolymer may be an isolated polymer,it is preferable that the copolymer is supplied as a raw material ofcosmetics in a form in which it is dissolved or dispersed in water or atleast one of hydrocarbon-based solvents, alcohol-based solvents,ester-based solvents, ketone-based solvents, silicone-based solvents andfluorine-containing solvents. The fluorine-containing copolymer iscontained in an amount of from 1 to 60% by weight, preferably from 1 to50% by weight, more preferably from 10 to 40% by weight relative to thetotal amount [the fluorine-containing copolymer plus (water or asolvent)]. When it is less than 1% by weight, the fluorine-containingcopolymer blended in a cosmetic preparation is too little, impartinginsufficient waterproofing property or water- and oil-repellency. Whenit is more than 60% by weight, the stability as a raw material isdeteriorated.

Hair cosmetics may contain the copolymer of the present invention in anamount of from 1 to 99% by weight, preferably from 2 to 50% by weight.

Examples of the hydrocarbon-based solvents include n-hexane, n-heptane,n-octane, n-nonane, n-decane, n-undecane, n-dodecane, isohexane,isoheptane, isooctane, isononane, isodecane, isoundecane, isododecane,cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, liquidparaffin, isoparaffin, toluene, benzene and xylene.

Examples of the alcohol-based solvents include ethanol and isopropylalcohol.

Examples of the ester-based solvents include butyl acetate, ethylacetate, amyl acetate and acyl acetate.

Examples of the ketone-based solvents include methyl ethyl ketone,methyl isobutyl ketone and acetone.

Examples of the silicone-based solvents includehexamethylcyclotrisiloxane (that is, a cyclic silicone trimer),octamethylcyclotetrasiloxane (that is, a cyclic silicone tetramer),decamethylcyclopentasiloxane (that is, a cyclic silicone pentamer),dodecamethylcyclohexasiloxane (that is, a cyclic silicone hexamer),dimethylpolysiloxane, methylphenylpolysiloxane and adimethylpolysiloxane/methyl(polyoxyethylene)sitoxane/ethyl(polyoxypropylene)siloxane copolymer.

Examples of the fluorine-containing solvents include hydrofluorocarbon(HFC), hydrofluoroether (HFE), fluoroether, fluorocarbon (FC) andnitrogen-containing fluorocarbon.

The HFC may be 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-4310),benzotrifluoride, m-xylene hexafluoride and the like.

The HFE may be represented by the general formula:

C_(n)H_(m)F₁OC_(x)H_(y)F_(z)

wherein n is a number of from 1 to 12, m is a number of from 0 to 25, 1is a number of from 0 to 11, m+1=2n+1, x is a number of from 1 to 12, yis a number of from 0 to 25, z is a number of from 0 to 11 and y+z=2x+1,provided that m and y are not simultaneously zero and 1 and z are notsimultaneously zero.

The HFE may be, for example, C₄F₉OCH₃ and C₄F₉OC₂H₅.

The fluoroether may be represented by the general formula:

(C_(n)F_(2n+1))₂O

wherein n is a number of from 3 to 5.

The fluoroether may be, for example, (C₃F₇)₂O and (C₄F₉)₂O

Examples of the FC include perfluorohexane, perfluorooctane,perfluorononane, perfluorobenzene, perfluorotoluene, perfluoroxylene,perfluorodecalin and perfluoromethyldecalin.

The nitrogen-containing fluorocarbon may be represented by the generalformula:

(C_(n)F_(2n+1))₃N

wherein n is a number of from 1 to 5.

The nitrogen-containing fluorocarbon may be, for example,perfluorotripropylamine and perfluorotributylamine.

These solvents may be used either alone or in admixtures. Solventshaving a property to evaporate easily at the skin temperature (about 30°C.) are preferred since they can provide a cool feeling during theirvolatilization and can form films on the skin easily. Particularly,octamethylcyclotetrasiloxane (that is, a cyclic silicone tetramer),decamethylcyclopentasiloxane (that is, a cyclic silicone pentamer),dimethylpolysiloxanes having viscosities of not greater than 10 cSt,which are silicone-based solvents, and isoparaffin, which is ahydrocarbon, are preferably used. In the case of using thefluorine-containing solvent, use of C₄F₉OCH₃, C₄F₉OC₂H₅, C₄F₉OC₃H₇ orC₄F₉OC₄H₉, which are HFEs, is most desirable. This type of solvents arevolatile and soluble in many solvents and oils widely used forcosmetics. They also have high solubilities of fluorine-containingpolymers.

The cosmetic of the present invention contains 0.1 to 30% by weight ofthe fluorine-containing copolymer as a main ingredient and may containat least 0.1% by weight of a fluorine compound-treated powder and/or afluorine-containing oil.

Moreover, the cosmetics of the present invention may compatibilize ordisperse the fluorine compound-treated powder and/or thefluorine-containing oil in a non-fluorine compound (for example, afluorine-free solvent) using the fluorine-containing copolymer as acompatibilizer or a dispersing agent.

The fluorine-containing oil may be a perfluoropolyether, ahydrofluoroether or a compound represented by the general formula:

wherein R^(1a) and R^(1d) represent a hydrogen atom or a partly orcompletely fluorinated aliphatic group having 1 to 20 carbon atoms,R^(1b) and R^(1c) represent a hydrogen atom, an aliphatic group having 1to 20 carbon atoms or a partly or completely fluorinated aliphatic grouphaving 1 to 20 carbon atoms, provided that at least one of R^(1a) toR^(1d) is a partly or completely fluorinated aliphatic group having 1 to20 carbon atoms, and n is a number of from 1 to 20, or by the generalformula:

wherein R^(2a) is a hydrogen atom or a partly or completely fluorinatedaliphatic group having 1 to 20 carbon atoms, R^(2b), R^(2c) and R^(2d)are an aliphatic group having 1 to 20 carbon atoms or a partly orcompletely fluorinated aliphatic group having 1 to 20 carbon atoms,provided that at least one of R^(2a) to R^(2d) is a partly or completelyfluorinated aliphatic group having 1 to 20 carbon atoms, and

m is a number of from 1 to 20.

Raw materials to be used for the cosmetics in which thefluorine-containing copolymer of the present invention is blended arenot particularly restricted as long as they are generally used forcosmetics.

For example, powders may be exemplified by inorganic powders such astalc, kaolin, mica, mica titanium, titanium oxide, iron oxide, magnesiumoxide, zinc monooxide, zinc dioxide, heavy or light calcium carbonate,calcium secondary phosphate, aluminum hydroxide, barium sulfate, silica,alumina, silica gel, carbon black, antimony oxide, magnesium silicatealuminate, magnesium metasilicate aluminate and synthesized mica; andorganic powders such as protein powder, fish scale foil, metal soap,polyvinyl chloride, nylon-12, microcrystalline fiber powder, tar pigmentand lake. These may be ones either untreated or treated with a siliconeor a fluorine compound. For example, the powder may be a fluorinecompound-treated powder.

Furthermore, examples other than powders include solid or semi-solidfats such as vaseline, lanoline, ceresin, microcrystalline wax, carnaubawax, candelilla wax, higher fatty acids and higher alcohols; liquid fatssuch as squalane, liquid paraffin, ester oil, diglyceride, triglycerideand silicone oil; fluorine-containing oils such as perfluoropolyether,perfluorodecalin and perfluorooctane; water-soluble or oil-solublepolymers, surfactants, colorants such as organic dyes, ethanol,antiseptics, antioxidants, colorant, thickeners, pH modifiers, perfumes,ultraviolet absorbers, humectants, blood circulation promoters, coldfeeling agents, antiperspirants, germicides and skin activators.

The cosmetic of the present invention can be produced in accordance withconventional methods and can be used as a finishing cosmetic such asfoundation, face powder, cheek color, eye color, mascara, eyeliner andnail color; basic cosmetics such as a milky lotion and cream; haircosmetics such as shampoo and rinse.

The copolymer for cosmetics of the present invention can be used forimproving the following drawbacks of fluorine compound-treated powders:

They have poor affinities with fluorine-free raw materials.

They have poor feelings in use, such as poor spread and poor adhesion.

They rise in the form of dust in the air during the production ofcosmetics.

They are poor in dispersibility in fluorine-free solvents.

The fluorine compound-treated powder to be treated with the copolymer ofthe present invention may be a powder treated with a fluorine-containingphosphate ester such as a fluorine-containing phosphate esterrepresented by the general formula:

[Rf—A—O]_(n)PO(OM)_(3−n)

wherein Rf represents a polyfluoroalkyl or perfluoropolyether grouphaving 6 to 16 carbon atoms, A represents an alkylene group having 1 to4 carbon atoms, or

wherein R¹ is an alkyl group having 1 to 4 carbon atoms and R² is analkylene group having 1 to 4 carbon atoms, or

M represents a hydrogen atom, a metal atom, ammonium or substitutedammonium and n represents a number of from 1 to 3.

An example is a fluorine compound-treated powder obtained by treatingpowders with 3 to 7% by weight, relative to the powders, of aperfluoroalkyl phosphate ester diethanolamine salt.

Examples of the fluorine compound-treated powder include those obtainedby treating powders, for example, inorganic or organic powders, withfluorine compounds. At least two powders may be mixed when they aresurface-treated with the copolymer. Moreover, at least two treatedpowders may be mixed also when they are blended to cosmetics.

The copolymer for cosmetics is made to be adhered to the surface of afluorine compound-treated powder by a wet method or a dry method, andthe wet method is preferred for uniform surface treatment. For example,a fluorine compound-treated powder is mixed in a solution prepared bydiluting either the copolymer itself or a solution of the copolymer withan organic solvent and stirred until the fluorine compound-treatedpowder gets wet uniformly with the organic solvent solution at roomtemperature or under heating. For the stirring in the above procedure, astirring device is used, for example, a Henschel mixer, a vibratory ballmill, a rotary ball mill, a supermixer and a planetary mixer. Instirring in a laboratory scale, a juicer for home use may be employed.The concentration of the copolymer in a solution in an organic solventis not particularly limited, but is adjusted so that the viscosity doesnot become too high during the stirring in the mixing of powder. Afterthe stirring, the organic solvent is removed under a vacuum condition orby heating and the treated powder is dispersed uniformly by means of theaforementioned stirring device. In stirring in a laboratory scale, ajuicer for home use or a speed cutter may be used.

The copolymer for cosmetics of the present invention can also be usedfor the improvement of the waterproofing property and the oil-repellencyof a silicone-treated powder. Examples of the silicone-treated powder tobe treated include one which has been treated withmethylhydrogenpolysiloxane by a wet method and one which has beentreated with 1,3,5,7-tetramethylcyclotetrasiloxane by a chemicalgas-phase vapor deposition method. Examples of a powder to be treatedfor the silicone-treated powder include talc, kaolin, mica, micatitanium, titanium oxide, iron oxide and zinc oxide, which are widelyused in cosmetics, as in the aforementioned fluorine-treated powder.When the silicone-treated powder is surface-treated with the copolymer,at least two silicone-treated powders may be mixed. Furthermore, alsowhen the treated powder is incorporated into the cosmetics, at least twosilicone-treated powders may be mixed.

Although the copolymer for cosmetics is adhered to the surface of thesilicone-treated powder by the wet method or the dry method as in theaforementioned fluorine-treated powder, the wet method is preferable foruniform surface-treatment.

In the powder coated with the copolymer of the present invention, theamount of the copolymer may be from 0.1 to 50% by weight, for example,from 1 to 30% by weight, based on the coated powder.

In the present invention, proper chemicals to improve the feeling in usemay, if needed, be used together in the surface-treatment. Examples ofthe chemicals to improve the feeling in use include lecithin,N-mono-long-chain-acyl basic amino acids, silicone, chitosan, collagenand wax.

Heretofore, since fluorine-containing oils typified byperfluoropolyether have poor affinities with fluorine-free rawmaterials, they are difficult to be blended into cosmetics. After theintensive study for overcoming the above problem, the present inventionfacilitates the blending of the fluorine-containing oils into cosmeticsby emulsifying the fluorine-containing oils in fluorine-free solventssuch as silicone-based solvents, hydrocarbon-based solvents, ester-basedsolvents and ketone-based solvents by using the fluorine-containing(meth)acrylate copolymers having specific composition as emulsifiers toform fluorine-containing oil/fluorine-free solvent type nonaqueousemulsions.

The present invention provides a cosmetic comprising a nonaqueousemulsion obtained by emulsifying a fluorine-containing oil in afluorine-free solvent using a copolymer for cosmetics as a emulsifier,wherein the fluorine-free solvent is any of a silicone-based solvent, ahydrocarbon-based solvent, an ester-based solvent and a ketone-basedsolvent, wherein the fluorine-containing oil is a perfluoropolyether, ahydrofluoroether, a compound represented by the general formula:

wherein R^(1a) and R^(1d) represent a hydrogen atom or a partly orcompletely fluorinated aliphatic group having 1 to 20 carbon atoms,

R^(1b) and R^(1c) represent a hydrogen atom, an aliphatic group having 1to 20 carbon atoms or a partly or completely fluorinated aliphatic grouphaving 1 to 20 carbon atoms, provided that at least one of R¹a to R^(1d)is a partly or completely fluorinated aliphatic group having 1 to 20carbon atoms, and

n is a number of from 1 to 20, or

by the general formula:

wherein R^(2a) is a hydrogen atom or a partly or completely fluorinatedaliphatic group having 1 to 20 carbon atoms,

R^(2b), R^(2c) and R^(2d) are an aliphatic group having 1 to 20 carbonatoms or a partly or completely fluorinated aliphatic group having 1 to20 carbon atoms, provided that at least one of R^(2a), to R^(2d) is apartly or completely fluorinated aliphatic group having 1 to 20 carbonatoms, and m is a number of from 1 to 20.

The amount of the emulsifier may be from 1 to 50 parts by weight, forexample, from 5 to 20 parts by weight, relative to 100 parts by weightof the fluorine-containing oil. The amount of the fluorine-free oil maybe from 50 to 10,000 parts by weight, for example, from 100 to 1,000parts by weight, relative to 100 parts by weight of thefluorine-containing oil.

In general, in the case wherein a large amount of oil-soluble polymer isblended into cosmetics, it is blended in the form of solution in avolatile solvent. This is because an oil-soluble polymer is difficult tobe converted into preparations since it is a solid or an elastic rubberymaterial. A volatile solvent typified by cyclic silicone and isoparaffinhas a superior ability of dissolving the oil-soluble polymer and canimpart superior functions to cosmetics, but it shows very strong skinirritation and can not be used in cosmetics for sensitive skins which isrequired to have low irritability. Therefore, a paste-form oil-solublepolymer which is easily converted into preparations has been demanded.The “paste-form” used herein means that a material has less fluidity atroom temperature and has such rheological properties that it can beeasily applied to the skin with a hand.

Although also in the present invention, most of the copolymers are solidor rubbery, fluorine-containing (meth)acrylate copolymers havingspecific compositions have been found to be in the paste-form after theintensive studies for overcoming the aforementioned problems.

The present invention also provides a cosmetic comprising a copolymercomprising a fluorine-containing (meth)acrylate and a silicon-containingpolymerizable compound, characterized in that the copolymer is in apaste-form and contains the fluorine-containing (meth)acrylate and thesilicon-containing polymerizable compound at a weight ratio of from 3/7to 7/3 and in that no volatile solvent is blended.

The composition of the copolymer may be a weight ratio of thefluorine-containing (meth)acrylate to the silicon-containingpolymerizable compound of from 3/7 to 7/3, for example, from 4/6 to 6/4.The addition of a proper amount of a solid or rubbery polymer to thecopolymer can vary the properties of the paste. The amount of thepaste-form copolymer is from 1 to 100% by weight, for example, from 2 to80% by weight relative to the whole cosmetic.

The present invention may use raw materials which is conventionally usedfor cosmetics except that the paste-form copolymer is contained as anessential ingredient and no volatile solvent is present. For example, inaddition to the copolymer, at least one of a powder, a high-boiling oil,a solid oil, water, a water-soluble polymer, an emulsifier and ahumectant may be blended.

The selection of fluorine-containing copolymers produced by polymerizingthe fluorine-containing (meth)acrylate and the silicon-containingpolymerizable compound as essential components results in cosmeticssatisfying the waterproofing property and water- and oil-repellencyderived from the fluorine-containing (meth)acrylate and thewaterproofing property, the water-repellency and the feelings in use(such as the “sleek feeling” and the “dry feeling”) derived from thesilicon-containing polymerizable compound. Furthermore, copolymerizingthe silicon-containing polymerizable compound facilitates the copolymerto dissolve in silicone oils widely used in cosmetics. When thecopolymer is blended into cosmetic preparations in which large amountsof fluorine-containing raw materials and silicone-containing rawmaterials are blended, the copolymer serves as a compatibilizer andimproves stability of the preparations.

Moreover, the selection of a fluorine-containing copolymer in whichalkyl (meth)acrylate, wherein the alkyl group preferably has 1 to 4carbon atoms, or an alkyl (meth)acrylate macromonomer, wherein the alkylgroup preferably has 1 to 22 carbon atoms, is polymerized in addition tothe fluorine-containing (meth)acrylate and the silicon-containingpolymerizable compound can improve the solubility of the copolymer inhydrocarbon-based solvents, ester-based solvents and ketone-basedsolvents. In particular, the use of the alkyl (meth)acrylatemacromonomer results in graft copolymers comprising fluorine-containing(meth)acrylate segments, silicon-containing polymerizable compoundsegments and alkyl (meth)acrylate macromonomer segments, wherebyimproving the solubility and exhibiting a high waterproofing propertyand high water- and oil-repellency at low fluorine concentrations. Whenthe copolymer is blended to cosmetic preparations in which thefluorine-containing raw materials, the silicone-containing raw materialsand the hydrocarbon-based, ester-based or ketone-based solvents, thecopolymer serves as a compatibilizer and improves the stability of thepreparations.

The selection of a fluorine-containing copolymer comprising apolyalkyleneglycol (meth)acrylate prevents make-up from coming offeasily even under the environment where sweat and sebum are presenttogether. Generally, the surface of a fluorine-containing copolymerwhich does not contain any hydrophilic monomer repels oil under dryconditions, but gets wet with oil when water is present together withoil [see “Surface property and application of fluoroalkyl acrylatepolymers”, Motonobu Kubo, SURFACE, 33, 185 (1995)]. To prevent this, ahydrophilic monomer, particularly polyethyleneglycol (meth)acrylate, maybe copolymerized. The amounts of sweat and sebum on the skin varydepending on the external environment. Fluorine-containing copolymerscontaining polyethyleneglycol (meth)acrylates show the water- andoil-repellency under any environment. However, the use of these monomerstends to cause some deterioration of the waterproofing property.

PREFERRED EMBODIMENT OF THE INVENTION

Examples of the present invention will be described, but Examples do notlimit the present invention.

PREPARATIVE EXAMPLE 1

In a four-neck flask equipped with a reflux condenser, a nitrogenintroduction tube, a thermometer and a stirrer, were placed 20 g ofCH₂═CHCOO(CH₂)₂(CF₂CF₂)_(n)CF₂CF₃ (hereinafter referred to as “FA”) (amixture of compounds wherein n is 3, 4 and 5 in a weight ratio of5:3:1), 20 g of a side-chain mercapto-modified silicone:

wherein m is from 10 to 200 and n is from 1 to 10 (KF-2001 manufacturedby Shin-Etsu Chemical Co., Ltd.) (hereinafter referred to as “Si-SH”)and 158 g of toluene, which were heated up to 60° C. and stirred for 30minutes under nitrogen flow. To this mixture was added 2 g of t-butylperoxypivalate (trade name: Perbutyl PV, manufactured by NOF Corp.) andpolymerization was carried out for 6 hours. By the gas chromatographyanalysis of the remaining FA in the reaction liquid, the polymerizationconversion of FA was found to be 95%. A precipitation was obtained fromthe resulting reaction liquid by using methanol and was vacuum-dried toisolate a FA/Si-SH (=5/5 wt.) copolymer. The measurement of a molecularweight of the resulting FA/Si-SH copolymer by GPC revealed that theweight average molecular weight was 20,000 (in terms of polystyrene).

PREPARATIVE EXAMPLE 2

By polymerization in the same manner as in Preparative Example 1 exceptthat 20 g of the monomer in Preparative Example 1, Si-SH, was replacedby 10 g of Si-SH and 10 g of n-butyl acrylate (BA), an FA/Si-SH/BA(=5/2.5/2.5 wt.) copolymer was produced. The copolymer had a weightaverage molecular weight of 35,000.

PREPARATIVE EXAMPLE 3

By polymerization in the same manner as in Preparative Example 1 exceptthat 20 g of the monomer in Preparative Example 1, Si-SH, was replacedby 20 g of both-ends-mercapto-modified silicone:

wherein n is from 10 to 20 (X-22-167B manufactured by Shin-Etsu ChemicalCo., Ltd.) (hereinafter referred to as “Si-DSH”), an FA/Si-DSH (=5/5wt.) copolymer was produced. The copolymer had a weight averagemolecular weight of 25,000.

PREPARATIVE EXAMPLE 4

By polymerization in the same manner as in Preparative Example 1 exceptthat 20 g of the monomer in Preparative Example 1, Si-SH, was replacedby 10 g of Si-DSH and 10 g of BA, an FA/Si-DSH/BA (=5/2.5/2.5 wt.)copolymer was produced. The copolymer had a weight average molecularweight of 22,000.

PREPARATIVE EXAMPLE 5

By polymerization in the same manner as in Preparative Example 1 exceptthat 20 g of the monomer in Preparative Example 1, Si-SH, was replacedby 10 g of azo group-containing silicone:

(VPS-0501 manufactured by Wako Pure Chemical Industries, Ltd.)(hereinafter referred to as “Azo-Si”) and 10 g of BA, an FA/Azo-Si/BA(=5/2.5/2.5 wt.) copolymer was produced. The copolymer had a weightaverage molecular weight of 24,000.

PREPARATIVE EXAMPLE 6

By polymerization in the same manner as in Preparative Example 1 exceptthat 20 g of the monomer in Preparative Example 1, Si-SH, was replacedby 20 g of 3-methacryloxypropyltrimethoxysilane:

(Sila-Ace S710 manufactured by Chisso Corp.) (hereinafter referred to as“TMS-MA”), an FA/TMS-MA (=5/5 wt.) copolymer was produced. The copolymerhad a weight average molecular weight of 21,000.

EXAMPLE 1 AND COMPARATIVE EXAMPLE 1

The copolymers produced in Preparative Examples 1, 2, 3, 4, 5 and 6 weredissolved in cyclic silicone pentamer (decamethylcyclopentasiloxane) orin isoparaffin (Isopar G manufactured by Exxon Chemical Corp.) so thatthe concentration of the polymers was 5% by weight. The interfacialtensions between these solutions (the concentrations of the copolymers:5 wt % in fluorine-free solvents) and perfluoropolyether (Demnum S-20manufactured by Daikin Industries, Ltd.) were measured by a spinningdrop method (a measuring device: Spinning Drop Tensiometer SITE-04manufactured by Krüss GmbH). As Comparative Example, interfacialtensions were measured in a similar manner using a fluorine-freeacryl-silicone copolymer [KP-545 manufactured by Shin-Etsu Chemical Co.,Ltd. (polymer composition: Si-MM/methyl methacrylate (MMA)/butylmethacrylate (BMA)/2-ethylhexyl acrylate(2EHA)═50/35/7.5/7.5 wt.)] and afluorine-modified silicone (FS-1265 manufactured by Toray Dow Corning).The results are shown in Table 1.

Si-MM in the acryl-silicone copolymer is a silicone macromonomerrepresented by the formula:

wherein Me is a methyl group.

TABLE 1 Interfacial tension (mN/m) Silicon- Ratio of containing Cyclicsilicone interfacial Ratio of interfacial compound Copolymer Compositionof copolymer pentamer tensions (%) Isoparaffin tensions (%)   — Nocopolymer was blended 5.43 — 5.58 — Si—SH Preparative FA/Si—SH = 5/5 wt.2.55 47 1.83 33 Example 1 Preparative FA/Si—SH/BA = 5/2.5/2.5 wt. 1.5529 1.73 31 Example 2 Si-DSH Preparative FA/Si-DSH = 5/5 wt. 2.78 51 1.7231 Example 3 Preparative FA/Si-DSH/BA = 5/2.5/2.5 wt. 1.52 28 1.22 22Example 4 Azo-Si Preparative FA/Azo-Si/BA = 5/2.5/2.5 wt. 2.22 41 1.7732 Example 5 TMS-MA Preparative FA/TMS-MA = 5/5 wt. 3.56 66 3.15 56Example 6 Comparative Acryl-silicone Si-MM/MMA/BMA/2EHA = 5.44 100  5.4998 Example 1 copolymer 50/35/7.5/7.5 wt. Fluorine- FS-1265 5.44 100 5.62 101  modified (Substituent: —CH₂CH₂CF₃) silicone

Blending the copolymers of the present invention into the fluorine-freesolvents decreased interfacial tensions to 20 to 60% of those detectedwhen nothing was blended. This attests the fact that the copolymers areadsorbed on the interfaces between the perfluoropolyether and thefluorine-free solvent. On the other hand, there was no decrease ininterfacial tension in Comparative Example 1. This shows that thefluorine-free acryl-silicone copolymer and the fluorine-modifiedsilicone were only dissolved in the fluorine-free solvents and had noabilities to be adsorbed on the interfaces.

EXAMPLE 2 AND COMPARATIVE EXAMPLE 2

The copolymers produced in Preparative Examples 1, 2, 3, 4, 5 and 6 weredissolved in HCFC-225 (CF₃CF₂CHCl₂) so that the concentration of thepolymers was 5% by weight and were formed into films on glass substratesby a cast method. The contact angles of water or liquid paraffin onthese coating films of the copolymers were measured. The fluorine-freeacryl-silicone copolymer and fluorine-modified silicone FS-1265 used inComparative Example 1 were also subjected to the same measurements. Theresults are shown in Table 2. The copolymers of the present inventionshowed higher contact angles than those of the Comparative Example 2.

TABLE 2 Contact angle of FA copolymer (°) Silicon- containingPreparative Composition of Liquid compound Example copolymer Waterparaffin Si—SH 1 FA/Si—SH = 5/5 wt. 121 82 2 FA/Si—SH/BA = 113 955/2.5/2.5 wt. Si—DSH 3 FA/Si—DSH = 5/5 wt. 120 81 4 FA/Si—DSH/BA = 11093 5/2.5/2.5 wt. Azo-Si 5 FA/Azo-Si/BA = 111 92 5/2.5/2.5 wt. TMS—MA 6FA/TMS—MA = 5/5 wt. 121 80 Comparative Acryl- Si—MM/MMA/BMA/ 101 41Example 2 silicone 2EHA = 50/35/7.5/ copolymer 7.5 wt. Fluorine- FS-1265(Substituent: 83 32 modified —CH₂CH₂CF₃) silicone

EXAMPLE 3 AND COMPARATIVE EXAMPLE 3

10 g of a perfluoropolyether (Demnum S-20 manufactured by DaikinIndustries, Ltd.) and 20 g of a 5% by weight solution of the copolymerobtained in Preparative Examples 1, 2, 3, 4, 5 or 6 in cyclic siliconepentamer (decamethylcyclopentasiloxane) or isoparaffin were emulsifiedwith an ultrasonic homogenizer for 1 minute. The copolymers produced inPreparative Examples 1, 2, 3, 4, 5 and 6 resulted in stablemicroemulsions having a particle size of from about 200 to 300 nm.However, in Comparative Example 3 [either a fluorine-free acryl-siliconecopolymer (KP-545 manufactured by Shin-Etsu Chemical Co., Ltd. (polymercomposition: Si-MM/methyl methacrylate/butyl methacrylate/2-ethylhexylacrylate=50/35/7.5/7.5 wt.)) or fluorine-modified silicone FS-1265 wasused as a copolymer], no emulsion was formed.

In the following Examples and Comparative Examples, cosmetics wereprepared using mixture powders shown in Table 3. The fluorine-treatedpowders (1) to (6) were those obtained by treating untreated powderswith 5% by weight, based on the untreated powders, ofperfluoroalkylethyl phosphate ester diethanol amine salt. Thesilicone-treated powders (7) to (9) were those obtained by treatinguntreated powders with 2% by weight, based on the untreated powders, ofmethylhydrogenpolysiloxane.

TABLE 3 Composition of mixture powder Type of raw material % by weight(1) Fluorine-treated titanium oxide 8.0 (2) Fluorine-treated yellow ironoxide 0.9 (3) Fluorine-treated red iron oxide 0.3 (4) Fluorine-treatedblack iron oxide 0.3 (5) Fluorine-treated talc 28.7 (6) Fluorine-treatedsericite 31.5 (7) Silicone-treated talc 3.8 (8) Silicone-treatedsericite 19.1 (9) Silicone-treated mica 7.4

Make-up lastingness (derived from the water- and oil-repellency of afilm), feelings in use (the “sleek feeling” and the “dry feeling”) and awaterproofing properly were evaluated according to the followingcriteria:

⊚: Very good

◯: Good

Δ: Average

X: Poor

X X: Very poor

The evaluation was done by five panelists specialized in functionalevaluation. The average of their evaluations was taken as the result. Asfor the waterproofing property, films formed by evenly coating materialson polyester films and leaving them for one day were used as testsamples. The waterproofing properties were evaluated from contact anglesof water on the films after immersing the films in water for one hourand then leaving them in the air for one day.

Cases wherein a contact angle is from 110 to 130° are indicated by “⊚”,those wherein a contact angle is from 90 to 109° are indicated by “◯”,those wherein a contact angle is from 60 to 89° are indicated by “Δ”,those wherein a contact angle is from 30 to 59° are indicated by “X ”,and those wherein a contact angle is less than 29° are indicated by “XX”.

EXAMPLE 4 AND COMPARATIVE EXAMPLE 4

The fluorine-treated powders (1) to (6), constituents of the mixturepowders shown in Table 3, were surface-treated with the FA/Si-SH (=5/5wt.) copolymer of Preparative Example 1by the following procedure. 40 gof a mixture of the fluorine-treated powders (1) to (6), 2 g of theFA/Si-SH copolymer and 100 g of toluene were mixed with a juicer mixerfor 30 seconds. The resulting mixture was placed in an aluminum vat anddried at 60° C. overnight. After drying, the residue was ground with aspeed cutter to give a fluorine-treated powder surface-treated with theFA/Si-SH copolymer.

In Comparative Example 4, a fluorine-treated powder was surface-treatedwith a fluorine-free acryl-silicone copolymer which was the same as inComparative Example 1, in place of the FA/Si-SH (=5/5 wt.) ofPreparative Example 1.

Powdery foundations were produced using 89.8% by weight of mixturepowder containing 69.7% by weight of the fluorine-treated powder whichhad been surface-treated with the aforementioned FA/Si-SH copolymer orfluorine-free acryl-silicone copolymer, 0.1% by weight ofparaoxybenzoate ester, 10% by weight of dimethylpolysiloxane and 0.1% byweight of a perfume.

The ingredients (1) or (2) and (3) were mixed and ground with anatomizer and then transferred to a Henschel mixer. To the mixture, theingredients (4) and (5) were added and mixed intimately. The resultantwas placed in a mold and press molded to give powdery foundations. Themake-up lastingness, waterproofing property and feelings in use of thepowdery foundations were evaluated. The results are shown in Table 4.

TABLE 4 Powdery foundation Comparative Type of raw material Example 4Example 4 (1) Copolymer-treated mixture powder 89.8 0 (2) Fluorine-freecopolymer-treated mixture 0 89.8 powder (3) Paraoxybenzoate ester 0.10.1 (4) Dimethylpolysiloxane 10.0 10.0 (5) Perfume 0.1 0.1 Make-uplastingness ⊚ Δ Water-proofing property ⊚ ◯ Feelings in use ⊚ ◯

The values in the table are indicated by “% by weight”.

EXAMPLES 5 to 9

The procedure of Example 4 was repeated except that the FA/Si-SH (=5/5wt.) copolymer used in Example 4 was replaced by the copolymers ofPreparative Example 2 (Example 5), of Preparative Example 3 (Example 6),of Preparative Example 4 (Example 7), of Preparative Example 5 (Example8), and of Preparative Example 6 (Example 9), respectively. In Examples5 to 9, all of the make-up lastingness, the waterproofing property andthe feeling in use were ⊚.

EXAMPLE 10 AND COMPARATIVE EXAMPLE 5

Nail colors were prepared in the compositions shown in Table 5. Theingredients (1) to (10) were mixed and stirred in a dispersion mill. Tothe mixture, the ingredient (11) or (12) was added and further mixed andstirred to give nail colors. The powder of the ingredient (11) wassurface-treated with the FA/Si-SH/BA (=5/2.5/2.5 wt) copolymer ofPreparative Example 2 in the same manner as Example 4. In ComparativeExample 5 was used a fluorine-treated powder which had beensurface-treated with, in place of the FA/Si-SH/BA (=5/2.5/2.5 wt)copolymer of Preparative Example 2, the fluorine-free acryl-siliconecopolymer which was the same as in Comparative Example 1. Thedispersibilities were evaluated according to the following criteria:

⊚: Very good

◯: Good

Δ: Average

X: Poor

X X: Very poor

TABLE 5 Nail color Example Comparative Type of raw material 10 Example 5(1) Nitrocellulose 9 9 (2) Alkyd resin 9 9 (3) Acetyltributyl citrate 33 (4) dl-Camphor 0.5 0.5 (5) Organic Bentonite 1.5 1.5 (6) Isopropylalcohol 5 5 (7) Ethyl acetate 10 10 (8) Butyl acetate 25 25 (9) Butanol4 4 (10) Toluene 31 31 (11) Fluorine-treated mica titanium surface- 2 —treated with FA/Si—SH/BA (= 5/2.5/2.5 wt.) copolymer (12)Fluorine-treated mica titanium surface- — 2 treated with fluorine-freeacryl-silicone copolymer Dispersibility ⊚ X

The values in the table are indicated by “% by weight”.

EFFECT OF THE INVENTION

The copolymer for cosmetics of the present invention can be easilyincorporated into conventional cosmetic preparations. The cosmetics inwhich the copolymer is blended therein can form films excellent in thewaterproofing property, water- and oil-repellency, feeling in use andsafety after the application to the skin.

Moreover, the copolymer for cosmetics serves as a compatibilizer forfluorine-containing raw materials and fluorine-free raw materials andhas an effect of stabilizing cosmetic preparations. Furthermore, thesurface treatment of fluorine compound-treated powders with thecopolymer for cosmetics can improve the following drawbacks of thefluorine compound-treated powders:

They have poor affinities with fluorine-free raw materials.

They have poor feeling in use, such as poor spread and poor adhesion.

They rise in the form of dust in the air during the production ofcosmetics.

They are poor in dispersibility in fluorine-free solvents.

What is claimed is:
 1. A copolymer comprising: (A) 5 to 99 parts byweight of repeating units derived from a fluorine-containing(meth)acrylate, and (B) 95 to 1 parts by weight of repeating unitsderived from at least one silicon-containing polymerizable compoundselected from the group consisting of a mercapto-modified silicone, anazo group-containing silicone and a polymerizable silane.
 2. Thecopolymer according to claim 1, further comprising (C) 1 to 50 parts byweight of repeating units derived from at least one fluorine-freemonomer selected from the group consisting of a polyalkyleneglycol(meth)acrylate, an alkyl (meth)acrylate macromonomer and an alkyl(meth)acrylate, in addition to the repeating units (A)and (B).
 3. Thecopolymer according to claim 1, wherein the fluorine containing(meth)acrylate is a compound represented by formula (I-1):

wherein Rf is a polyfluoroalkyl or perfluoropolyether group having 6 to16 carbon atoms, A is an alkylene group having 1 to 4 carbon atoms or

wherein R¹ is an alkyl group having 1 to 4 carbon atoms and R³ is analkylene group having 1 to 4 carbon atoms, or

and X is a hydrogen atom or a methyl group, or a fluorine-containing(meth)acrylate macromonomer represented by formula (I-2):

wherein Rf is a polyfluoroalkyl or petfluoropolyether group having 6 to16 carbon atoms, A¹ is an alkylene group having 1 to 4 carbon atoms or

wherein R¹ is an alkyl group having 1 to 4 carbon atoms and R² is analkylene group having 1 to 4 carbon atoms, or

X¹¹ is a hydrogen atom or a methyl group, Y¹¹ is a hydrogen atom or amethyl group, and m is from 5 to
 100. 4. The copolymer for cosmeticsaccording to claim 1, wherein the mercapto-modified silicone isrepresented by the general formula:

wherein R¹ is a divalent saturated hydrocarbon group having 1 to 10carbon atoms having a linear or branched carbon chain which may beintervened by one or two ether linkages, 1 is from 10 to 20, m is from10 to 200 and n is from 1 to
 10. 5. The copolymer according to claim 1,wherein the azo group-containing silicone is represented by the formula:

wherein x is from 10 to 200 and n is from 1 to
 20. 6. The copolymeraccording to claim 1, wherein the polymerizable silane is represented bythe formula:

or CH₂═CHSi (OR³)₃ wherein R¹ is a methyl group or a hydrogen atom, R²is a divalent saturated hydrocarbon group having 1 to 10 carbon atomshaving a linear or branched carbon chain which may be intervened by oneor two ether linkages, and R³ is an alkyl group having 1 to 4 carbonatoms.
 7. The copolymer according to claim 2, wherein thepolyalkyleneglycol (meth)acrylate is represented by formula (III-1):CH₂═CR¹¹COO—(R¹²—O)_(n)—R¹³  (III-1) wherein R¹¹ and R¹³ are a hydrogenatom or a methyl group, R¹² is an alkylene group having 2 to 6 carbonatoms, and n is an integer of from 1 to
 50. 8. The copolymer accordingto claim 2, wherein the alkyl (meth)acrylate macromonomer is representedby formula (III-2):

wherein X²¹ and Y²¹ are independently a hydrogen atom or a methyl group,n is from 1 to 22, and m is from 5 to
 100. 9. The copolymer according toclaim 1, wherein the alkyl (meth)acrylate is represented by formula(III-3):

wherein X is a hydrogen atom or a methyl group, and n is from 1 to 22.10. A cosmetic composition comprising the copolymer according to any oneof claims 1 to 9 dissolved or dispersed in a medium.
 11. A cosmeticcomposition comprising 1 to 60% by weight of the copolymer according toany one of claims 1 to 9 dissolved or dispersed in a medium.
 12. Thecosmetic composition according to claim 11, wherein the medium is wateror at least one organic solvent selected from the group consisting of ahydrocarbon-based solvent, an ester-based solvent, a ketone-basedsolvent, an alcohol-based solvent, a silicone-based solvent and afluorine-containing solvent.
 13. The cosmetic composition according toclaim 12, wherein the fluorine-containing solvent is a hydrofluoroetherrepresented by the formula: C_(n)H_(m)F_(/)OC_(x)H_(y)F_(z) wherein n isa number of from 1 to 12, m is a number of from 0 to 25, / is a numberof from 0 to 11, m+/=2n+1, x is a number of from 1 to 12, y is a numberof from 0 to 25, z is a number of from 0 to 11 and y+z=2x+1, providedthat m and y are not simultaneously zero and / and z are notsimultaneously zero.
 14. A cosmetic composition comprising 0.1 to 30% byweight of the copolymer according to claim 1 as an essential componentand additionally containing at least 0.1% by weight of a fluorinecompound-treated powder and/or a fluorine-containing oil.
 15. A cosmeticcomposition comprising a fluorine compound powder and/or afluorine-containing oil compatibilized or dispersed into a fluorine-freecompound with the copolymer according to claim 1 as a compatibilizingagent or a dispersing agent.
 16. A cosmetic composition comprising afluorine compound powder surface-treated with the copolymer according toclaim
 1. 17. The cosmetic according to any one of claims 14 to 16,wherein the fluorine compound-treated powder is a powder treated with afluorine-containing phosphate ester represented by the general formula:[Rf—A—O]_(n)PO(OM)_(3−n) wherein Rf represents a polyfluoroalkyl orperfluoropolyether group having 6 to 16 carbon atoms, A represents analkylene group having 1 to 4 carbon atoms, or

wherein R¹ is an alkyl group having 1 to 4 carbon atoms and R² is analkylene group having 1 to 4 carbon atoms, or

M represents a hydrogen atom, a metal atom, ammonium or substitutedammonium, and n represents a number of from 1 to
 3. 18. The cosmeticaccording to claim 14 or 15, wherein the fluorine-containing oil is aperfluoropolyether, a hydrofluoroether or a compound represented by thegeneral formula:

wherein R^(1a) and R^(1d) represent a hydrogen atom or a partly orcompletely fluorinated aliphatic group having 1 to 20 carbon atoms,R^(1b) and R^(1c) represent a hydrogen atom, an aliphatic group having 1to 20 carbon atoms or a partly or completely fluorinated aliphatic grouphaving 1 to 20 carbon atoms, provided that at least one of R^(1a) toR^(1d) is a partly or completely fluorinated aliphatic group having 1 to20 carbon atoms, and n is a number of from 1 to 20, or by the generalformula:

wherein R^(2a) is a hydrogen atom or a partly or completely fluorinatedaliphatic group having 1 to 20 carbon atoms, R^(2b), R^(2c) and R^(2d)are an aliphatic group having 1 to 20 carbon atoms or a partly orcompletely fluorinated aliphatic group having 1 to 20 carbon atoms,provided that at least one of R^(2a) to R^(2d) is a partly or completelyfluorinated aliphatic group having 1 to 20 carbon atoms, and m is anumber of from 1 to
 20. 19. A cosmetic composition comprising a siliconepowder surface treated with the copolymer for cosmetics according toclaim
 1. 20. A cosmetic composition comprising a fluorine-containing oilin a fluorine-free solvent emulsified in a nonaqueous emulsion with acopolymer for cosmetics as an emulsifier, wherein the copolymer forcosmetics is the copolymer according to claim 1 or 2, the fluorine-freesolvent is any one of a silicone-based solvent, a hydrocarbon-basedsolvent, an ester-based solvent and a ketone-based solvent, thefluorine-containing oil is a perfluoropolyether, a hydrofluoroether, ora compound represented by the formula:

wherein R^(1a) and R^(1d) represent a hydrogen atom or a partly orcompletely fluorinated aliphatic group having 1 to 20 carbon atoms,R^(1b) and R^(1c) represent a hydrogen atom, an aliphatic group having 1to 20 carbon atoms or a partly or completely fluorinated aliphatic grouphaving 1 to 20 carbon atoms, provided that at least one of R^(1a) toR^(1d) is a partly or completely fluorinated aliphatic group having 1 to20 carbon atoms, and n is a number of from 1 to 20, or by the formula:

wherein R^(2a) is a hydrogen atom or a partly or completely fluorinatedaliphatic group having 1 to 20 carbon atoms, R^(2b), R^(2c) and R^(2d)are an aliphatic group having 1 to 20 carbon atoms or a partly orcompletely fluorinated aliphatic group having 1 to 20 carbon atoms,provided that at least one of R^(2a) to R^(2d) is a partly or completelyfluorinated aliphatic group having 1 to 20 carbon atoms, and m is anumber of from 1 to 20.